Cyanine dyes



United States Patent 23 Claims ABSTRACT OF THE DISCLOSURE Cyanine dyes are provided which feature an imidazo- [4,5-blquinoxaline nucleus. Light sensitive emulsions containing such dyes are also provided.

This application is a continuation-in-part of our copending application Ser .NO. 573,183, filed Aug. 18, 1966, and now abandoned, which is a continuation-in-part of our copending application Ser. N0. 286,469, filed June 10, 1963, and now abandoned.

This invention relates to polymethine dyes, and more particularly to new cyanine dyes, intermediates and methods for preparing these new dyes, to photographic emulsions containing these dyes, and to the use of these dyes as bleachable filter dyes and as biological stains.

It is, accordingly, an object of the invention to provide a new class of polymethine dyes that function as desensitizers or light absorbing dyes for photographic elements. Another object is to provide a new class of chemical intermediates from which these new dyes can be derived. Another object is to provide photographic silver halide emulsions containing these new dye compounds as desensitizers. Another object is to provide methods for preparing these new compounds and photographic materials thereof. Other objects will become opparent hereinafter from a consideration of the description and examples.

In accordance with one embodiment of this invention, cyanine dyes are provided which contain an imidazo [4,5-bl-quinoxaline salt moiety.

In another embodiment of this invention, cyanine dye salts are provided which comprise two nuclei joined to gether by methine linkage, one of the nuclei being an imidazo[4,5-b]quinoxaline nucleus, which is joined through the 2-carbon atom thereof to the met-hine linkage, and a second nucleus to complete the cyanine dye. Advantageously, the second nucleus of such dyes contains a heterocyclic nitrogen atom, and the methine linkage is part of a polyene chain containing an equal number of alternating single and double bonds, one terminal carbon atom of the polyene chain being the 2-carbon atom of an imidazo[4,5-b]quinoxaline nucleus, the other terminal carbon atom of the polyene chain being in the second nucleus and attached to the heterocyclic nitrogen atom. Preferably, the second nucleus in these dyes is a desensitizing nucleus. As used herein and in the appended claims, desensitizing nucleus refers to those nuclei which, when converted to a symmetrical carbocyanine dye and added to a gelatin silver chlorobromide emulsion containing 40 mole percent chloride and 60 mole percent bromide, at a concentration of from 0.01 to 0.2 gram dye per mole of silver, cause, by electron trapping, at least an 80% loss in the blue speed of the emulsion when it is sensitometrically exposed and developed 3 minutes at 20 C. in Kodak developer D19. Preferably, the desensitizing nuclei are those which, when converted to a symmetrical carbocyanine dye and tested as just described, essentially completely desensitize the test emulsion to 3,43 1,1 l 1 Patented Mar. 4, 1969 blue radiation. Substantially complete desensitization as used herein refers to nuclei which, when tested as described above, result in at least about a and preferably more than a loss of speed to blue radiation. Nitro-substituted heterocyclic nuclei of the type used in cyanine dyes are typical desensitizing nuclei.

In another embodiment of the invention, merocyanine dyes are provided comprising two nuclei joined together through an acyclic methine group which is part of a polyene chain containing an equal number of alternating single and double bonds, one of the terminal atoms of the polyene chain being the 2-carbon atom of an imidazo [4,5-b]quinoxaline nucleus, and the other terminal carbon atom of the polyene chain being in a second hetero cyclic ring and attached to on extracyclic carbonylic oxygen atom.

In still another embodiment of this invention, styryl dyes are provided comprising an imidazo[4,5-b]quinoxaline nucleus joined to a para-alkylamino benzene ring through an acyclic polyene chain containing an equal number of single and double bonds, one terminal atom of the polyene chain being the Z-carbon atom of said imidazo[4,5-b1quinoxaline nucleus, the other terminal carbon atom being in the benzene ring and attached to the nitrogen atom of the para-aminoalkyl group.

In a further embodiment of this invention, cyanine dyes are provided comprising two imidazo [4,5-b1quinoxaline nuclei joined together through a polyene chain containing an equal number of alternating single and double bonds, the terminal carbon atoms of the polyene chain being the 2-carb0n atoms, respectively, of the imidazo [4,5-b1quinoxaline nuclei. Preferably, the polyene chain of these dyes is composed of five carbon atoms.

The new dyes of the invention include those represented by the following general formulas:

wherein n represents a positive integer of from 1 to 4, m and g each represents a positive integer of from 1 to 2, d represents a positive integer of from 1 to 3, R

dinedione, 1,3 dipbenyl 2 thio-2,4-imidazolidinedione, etc.) a 2-imidaZolin-5-one nucleus (e.g., 2-propylmercapto-2-imidazolin-5-one, etc.), etc. (especially useful are nuclei wherein Q represents a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom, and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom).

The imidazo[4,5-b]quinoxaline nucleus in the dyes of this invention can contain various substituents, such as at least one halogen substituent, e.g., chloro or bromo, dichloro, etc.; nitro; cyano; or, a fused aryl ring (such as phenyl) to provide, for example, an 8H-benzo[f]imidazo [4,5-b]quinoxaline nucleus. Dyes which contain a nitro, a monoor a di-chloro substituted imidazo[4,5-b]quinoxaline nucleus are of particular advantage in fogged, direct positive photographic silver halide emulsions. Such nitro or chloro-substituted dyes have an unexpectedly sharp adsorption peak and in addition impart an unexpected increase in speed to such emulsions. Halogen substituted dyes (such as chloro substituted dyes) provide unexpected improved overall results (as compared to the non-halogen substituted analogs) in direct positive emulsions with respect to speed, higher D max. or lower D min.

The above defined dye compounds are power desensitizers for light-sensitive photographic silver halide emulsions and may be used when desensitization by means of dyes is required. The dyes absorb strongly and sharply, and their colors are uniform and deep. A number of them are bleachable by photographic developers and may thus also be used as bleachable dyes in filter layers or backing layers in photographic elements. The dye compounds can also be used as biological stains.

In accordance with the invention, we prepare the dye compounds defined by the above Formulas I, II, III and IV from our new imidazo[4,5-b]quinoxalinium salt intermediates represented by the formula:

wherein R, R and X are as previously defined and R represents a member selected from an alkyl group of from 1-4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, etc., or benzyl, phenylethyl, or an aryl group, e.g., phenyl, p-tolyl, etc. In general, our dyes are produced by heating a mixture of a quaternary salt of above Formula V with the appropriate intermediate. The reaction mixtures are heated to advantage in any of the suitable solvents used in dye synthesis including solvents such as ethanol, propanol, dioxane, pyridine, quinoline, and the like, at temperatures up to the reflux temperature of the mixture. Advantageously, the reaction is carried out in the presence of a basic condensing agent such as a pyridine or an amine, e.g., trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylaniline, N, N-diethylaniline, etc.

The symmetrical cyanine dyes of Formula I are prepared to advantage by heating a mixture of a compound of Formula V (in which R is methyl) with diethoxymethyl acetate (forms carbocyanine), triniethoxypropene (forms dicarbocyanine), l-anilino-S-phenylimino-1,3-pentadiene hydrochloride (forms tricarbocyanine), etc., pref erably in a solvent and in the presence of a basic condensing agent such as mentioned above, if desired.

The unsymmetrical cyanine dyes of Formula II are prepared advantageously by heating a mixture of a compound of Formula V (in which R is methyl) with a com pound of the formula:

wherein R X and Z are as previously defined, g and q each represents a positive integer of from 1 to 2, R represents an aryl group of from 6-7 carbon atoms, e.g., phenyl, ptolyl, etc., and R represents an alkyl group of from 1-12 carbon atoms. This is preferably carried out in a suitable solvent and in the presence of a basic condensing agent.

The styryl dyes of Formula III are prepared to advantage by heating a mixture of a compound of Formula V (in which R is methyl) with the appropriate N,N-disu'bstituted p-aminobenzaldehyde, or N,N-disubstituted paminocinnamaldehyde preferably in a suitable solvent and in the presence of a basic condensing agent.

Our mercocyanine dyes of Formula IV are made to advantage by heating a mixture of a compound of Formula V (in which R is methyl) with a compound of the formula:

Example 1.1,1',3,3'-tetraethylimidazo[4,5-b] quinoxalinocarbocyanine chloride A mixture of 2.8 g. (2 mols.) of 1,3-diethyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 1.5 g. (1 mol. plus excess) of diethoxymethylacetate in 10 ml. of pyridine was refluxed 10 minutes. After chilling, the reaction mixture was filtered and the solid washed with ethyl alcohol. After two recrystallizations from ethyl alcohol, 0.9 g. (34%) of pure dye was obtained as dark crystals with. a bright reflex, M.P. 250252 dec. It was bleachable by photographic developers, i.e., developer solutions, such as Kodak developer D-76.

Example 2.l,l,3,3'-tetraethylimidazo[4,5-b] quinoxalinodicarbocyanine chloride A mixture of 2.8 g. (2 mols.) of 1,3-diethyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 1.6 g. (1 mol. plus 100% excess) of 1,1,3-trimethoxypropene in 10 ml. of pyridine was refluxed 10 minutes. After chilling, the reaction mixture was filtered and the solid washed with ethyl alcohol. After two recrystallizations from ethyl alcohol, 1.1 g. (40%) of pure dye was obtained as green crystals, M.P. 231-232 dec. It was bleachable by photographic developers.

Example 3 .-1 ,3 ,3'-triethylimidazo[4,5-b] quinoxalinooxacarbocyanine iodide Example 4.1,3,3'-triethylimidazo [4,5-b1quinoxalinothia-carbocyanine iodide A mixture of 1.4 g. (1 mol.) of 1,3-diethyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 2.25 g. (1 mol.) of 2-fi-acetanilidovinyl-3-ethylbenzothiazolium iodide in 10 ml. of ethyl alcohol and 0.5 g. (1 mol.) of triethylamine was refluxed 15 minutes. After chilling, the reaction mixture was filtered and the solid washed with ethyl alcohol. After two recrystallizations from methyl alcohol, 1.15 g. (41%) of pure dye was obtained as green crystals with a golden reflex, M.P. 284-285 dec. It was bleacha ble by photographic developers.

Example 5 .1,3-diethyl-1,3',3'-trimethylimidazo [4,5-b] quinoxalinoiudocarbocyanine iodide A mixture of 1.4 g. (1 mol.) of 1,3-diethyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 2.2 g. (1 mol.) of Z-fl-acetanilidoviuyl-1,3,3-trimethyl-3H-indolium iodide in ml. of ethyl alcohol and 0.5 g. (1 mol.) of triethylamine was refluxed minutes. After chilling, the reaction mixture was filtered and the solid washed with ethyl alcohol. After two recrystallizations from methyl alcohol, 0.8 g. (29%) of pure dye was obtained as green needles, M.P. 273274 dec. It was bleachable by photographic developers.

Example 6.1,3-diethyl-3-methylimidazo [4,5-b]quinoxalino-thiazolin0-carbocyanine iodide A mixture of 1.4 g. (1 mol.) of 1,3-diethyl-2-methylimidazo [4,5-b1quinoxalinium chloride and 1.8 g. 1 mol.) of 2- 8-anilinovinyl-3-methylthiazolinium iodide in 10 ml. of ethyl alcohol was treated with 0.5 g. (1 mol.) of acetic anhydride and 1 g. (2 mols.) of triethylamine and the mixture was refluxed 15 minutes. After chilling, the reaction mixture was filtered and the solid washed with ethyl alcohol. After two recrystallizations from methyl alcohol, 1.1 g. (44%) of pure dye was obtained as brown crystals, M.P. 281282 dec. It was bleachable by photographic developers.

Example 7.-1,1,3-triethylimidazo[4,5-b] quinoxalino-2'- carbocyanine iodide A mixture of 1.4 g. (1 mol.) of 1,3-diethyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 2 g. (1 mol.) of Z-fl-anilinovinyl-l-ethylquinolinium iodide in 10 ml. of ethyl alcohol was treated with 0.5 g. (1 mol.) of acetic anhydride and l g. .(2 mols.) of triethylamine and the mixture was refluxed 15 minutes. After chilling, the reaction mixture was filtered and the solid washed with ethyl alcohol. The solid was extracted three times with methyl alcohol, and the residue recrystallized from pyridine. The pure dye was obtained in a 5% yield as dull green crystals, M.P. 291292 dec. It was bleachable by photographic developers.

Example 8.-2-p-dimethylaminostyryl-1,3-diethylimidazo[4,5-b1quinoxalinium iodide N 011 3 TI \N/\N/ OH:

A mixture of 1.4 g. (1 mol.) of 1,3-diethyl-2-methyl imidazo[4,5-b]quinoxalinium chloride and 1 g. (1 mol. plus 33% excess) of p-dimethylaminobenzaldehyde in 10 ml. of ethyl alcohol and 3 drops of piperidine was refluxed 1 hour. After chilling the reaction mixture was filtered and the solid washed with ethyl alcohol. The filtrate was treated with a solution of 3 g. of sodium iodide in 5 ml. of water. After chilling, the mixture was filtered and the solid washed with ethyl alcohol. After two recrystallizations from methyl alcohol, 0.5 g. of pure dye was obtained as green crystals with a golden reflex, M.P. 262-263 dec. It was bleachable by photographic developers.

Example 9.-5- 1,3-diethylimidazo [4,5 -b] quinoxalin-2-ylidene) ethylidene] -3-ethylrhodanine A mixture of 2.8 g. (1 mol.) of 1,3-diethyl-2-methylimidazo[4,5-b]quinoxalinium chloride and 3 g. (1 mol.) of S-acetanilidomethylene-3-ethylrhodanine in 15 ml. of pyridine and 1 g. of triethylamine was refluxed 45 minutes. The reaction mixture was diluted with ml. of ethyl alcohol and chilled. The solid was filtered off and washed with ethyl alcohol. The crude dye was dissolved Example 10.-- 1,3-diethylimidazo [4,5-b] quinoxalin-2- 5 ylidene) ethylidene] -1,3-diethyl-2-thiobarbituric acid A mixture of 1.4 g. (1 mol.) of 1,3-diethyl-2-methyl imidazo[4,5-b]quinoxalinium chloride and 1.5 g. (1 mol.) of S-anilinomethylene-1,3-diethyl-2-thiobarbituric acid in ml. of pyridine was treated with 0.5 g. (1 mol.) of acetic anhydride and 1.0 g. (2 mols.) of triethylamine and the mixture refluxed 45 minutes. The reaction mixture was diluted with 50 ml. of ethyl alcohol and chilled. The solid was filtered oil? and washed with ethyl alcohol. The crude dye was dissolved in pyridine was precipitated with methyl alcohol. The solid was Washed with decantation several times with ethyl ether. The remaining solid was dissolved in pyridine and precipitated with methyl alcohol. An 18% yield of pure dye was obtained as maroon crystals with a silvery reflex, M.P. 320. It was not bleachable by photographic developers.

Example 1 1.-1,3-diethyl-2-methylimidazo [4,5 -b] quinoxalinium chloride To a solution of 32.4 g. (1 mol.) of 2,3-bis(ethylamino)quinoxaline [Hinsberg and Schwantes, Ber. 36, 4050 (1903)] in 125 ml. of dimethylacetarnide was added 24 g. (1 mol. plus 100% excess) of acetyl chloride in small portions with shaking. After the addition was complete, the solid reaction product was heated and the solid dissolved. The solution was refluxed 20 minutes and then cooled. After adding 300 ml. of acetone the mixture was r chilled. The solid was filtered 0E and washed with acetone. A yield of 17.8 g. (43%) was obtained, M.P. 198- 200 dec. Reworking the filtrates yielded an additional 12 g. (28% In place of the 2,3-bis(ethylamino)quinoxaline in the above example, there may be substituted an equivalent amount of other related quinoxalines, for example, 2,3- bis (methylamino)-quinoxaline to give 1,2,3-trimethylimidazo[4,5-b]quinoxalinium chloride, or 2,3-bis (propylamino)quinoxaline to give 1,3-dipropyl-2-methylimidazo [4,5-b]quinoxalinium chloride, or 2,3-bis(butylamino) quinoxaline to give 1,3 dibutyl-2-methylimidazo-[4,5-b] quinoxalinium chloride, etc. Also, in place of the acetyl chloride in the above example, there may be substituted an equivalent amount of related acyl chlorides, for example, propionyl chloride to give the corresponding 1,2,3- triethylimidazo[4,5-b1quinoxalinium chloride, or butyryl chloride to give the. corresponding l,3-diethyl-2-propylimidazo[4,5-b]quinoxalinium chloride, or valeryl chloride to give the corresponding 1,3-diethyl-2-butylimidazo [4,5-b]quinoxaliniurn chloride, and the like'. It will also 70 be understood that any other of the mentioned starting 2,3-bis(alkylamino)quinoxalines will give with propionyl chloride, butyryl chloride or valeryl chloride the corresponding 1,3 dialkyl 2 alkylimidazo[4,5 b]quinoxalinium chlorides.

10 Example 12.-1,l',3,3'-tetra(2-hydroxyethyl)imidazo [4,5-b1quinoxalinocarbocyanine iodide /N HOCHzCHz A mixture of 8.8 g. (2 mols.) of 1,3-di(2-hydroxyethyl) Z-methylirnidazo [4,5-bJquinoxalinium p toluenesulfonate, 2 g. (1 mol.+25% excess) of diethoxymethyl acetate, and 15 ml. of pyridine was refluxed ten minutes. The reaction mixture was chilled and then filtered. The filtrate was treated with ether and the oily layer separated from the supernatant liquid by decantation, and then washed with ether. The oily layer was stirred with a small amount of ethyl alcohol and chilled. The solid was collected on a filter and Washed with ethyl alcohol. The filtrate was treated with an aqueous solution of five grams of sodium iodide. The crude dye was collected on a filter and washed with Water. After recrystallization from methyl alcohol, 0.2 g. (3%) of pure dye was obtained as green crystals, M.P. 254-255 dec.

N HOCHzCH: CH:

A mixture of 4.4 g. (1 mol.) of 1,3-di(2-hydroxyethyl) 2-methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 4.4 g. (1 mol.) of 2-acetanilidovinyl-1,3,3- trimethyl-BH-indolium iodide, 15 ml. of ethyl alcohol, and 1 g. of triethylamine was refluxed 30 minutes. The reaction mixture was chilled and treated with ether. The oily layer was separated from the supernatant liquid and washed with ether and then with Water. The residue was titrated with ethyl alcohol and chilled. The crude dye was collected on a filter and washed lightly with ethyl alcohol. After recrystallization from methyl alcohol, 1.1 g. (19%) of pure dye was obtained as green crystals, M.P. 273-274 dec.

Example 14.--2-pdimethylaminostyryl-1,3-di(2-hydroxyethyl) imidazo [4,5-b] quinoxalinium p-toluenesulfonate 1 1 Example 15.-1,1',3 ,3 '-tetraallylimidazo [4,5 -b] quinoxalinocarb ocyanine p-toluenesulfonate CHpCH-CHz CHz-CH=CH2 CHFCH-CH: I CzH6 A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2-methylimidazo[4,5-b1quinoxalinium p-toluenesulfonate, 2.2 g. (1 mol.) of Z-fi-acetanilidovinyl-B-ethylbenzoxazolium iodide, 10 ml. of ethyl alcohol, and 0.5 g. (1 mol.) of triethylamine lwas refluxed ten minutes. The reaction mixture was chilled and the crude dye was collected on a filter and washed with ethyl alcohol and then with water. After recrystallization from methyl alcohol, 1.6 g. (57%) of pure dye was obtained as dark crystals with a shiny reflex, M.P. 253254 dec.

Example 17.--1,3-diallyl-3'-ethylimidazo[4,5-b] quinoxalinoethiacarbocyanine iodide c H =C H-C H2 A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2-methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 2.25 g. (1 mol.) of Z-B-acetanilidovinyl-3-ethylbenzothiazolium iodide, 10 ml. of ethyl alcohol, and 0.5 g. (1 mol.) of triethylamine was refluxed ten minutes. The reaction mixture was chilled and the crude dye was collected on a filter and washed with ethyl alcohol and then with water. After recrystallization from methyl alcohol, 2.0 g. (69%) of pure dye was obtained as dark green crystals, M.P. 250-251 dec.

Example 1 8.-1,3-diallyl-l,3,3- triunethylimidazo[4,5-b] quinoxalinoindocarbocyanine iodide CHFCHCH1 CH;

CHz=CH-CH2 1 CH:

A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2-methylimidazo[4,5-b1quinoxalinium p-toluenesulfonate, 2.25 g. (1 mol.) of 2-fi-acetani1idovinyl-1,3,3-trimethyl-3H-indolium iodide, 10 ml. of ethyl alcohol, and 0.5 g. (1

mol.) of triethylamine was refluxed ten minutes. The reaction mixture was chilled and the crude dye collected on a filter and washed with ethyl alcohol. After recrystallization from methyl alcohol, 1.4 g. (48%) of pure dye was obtained as green crystals with a shiny reflex, M.P. 246- 247 dec.

Example 19.1,3-dial1yl-3'-ethyl-4,5'-benzoimidazo[4, 5-b]quinoxalino thiacarbocyanine p-toluenesulfonate A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2-methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 2.5 -g. (1 mol.) of 2-fi-anilinovinyl-l-ethylnaphtho[ 1,2-d]thiazolium p-toluenesulfonate, 15 ml. of ethyl alcohol, 0.5 g. (1 mol.) of acetic anhydride, and 1 g. (2 mols.) of triethylamine was refluxed 15 minutes. The reaction mixture was chilled and the crude dye was collected on a filter and washed with ethyl alcohol. After recrystallization from methyl alcohol, 1.8 g. (57%) of pure dye was obtained as green needles with a shiny reflex, M.P. 243 244 dec.

Example 20.-1,3-diallyl-l'-ethylimidazo[4,5-b]quinoxalino-2-carbocyanine iodide A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2-methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 2 g. (1 mol.) of 2-,B-anilinovinyl-l-ethylquinolinium iodide, 20 m1. of acetic anhydride and 1 -g. (2 mols.) of triethylamine was stirred for 3 hours at room temperature. The reaction mixture was chilled, and the crude dye was collected on a filter and then washed with acetic anhydride, then with water and then with acetone. After recrystallization from methyl alcohol, 1 g. (34%) of pure dye was obtained as green crystals with a shiny reflex, M.P, 261-262 dec.

Example 21.--1,3-diallyl-2-p-dimethylaminostyrylimidazo [4,5-b]quinoxalinium p-tolueuesulfonate CH CHCHz A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1 g. (1 mol.+33% excess) of p-dimethylaminobenzaldehyde, and 15 ml. of acetic anhydride was refluxed five minutes. The reaction mixture was chilled and the crude dye collected on a filter and washed with acetic anhydride. After recrystallization from ethyl alcohol, 1.3 g. (45%) of pure dye was obtained as green crystals with a bright reflex, M.P. 238239 dec.

Example 22.- 1,3-diallylimidazo [4,5 -b] quinox-alin- 2 3H) -ylidene ethylidene] 3-ethylrhodanine O Hz=C H- O H:

A mixture of 2.2 g. (1 mol.) of 1,3-diallyl-2-methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1.6 g. (1 mol.) of 5-acetanilidomethylene-3-ethylrhodanine, and m1. of pyridine was refluxed ten minutes and then ml. of methyl alcohol was added. The reaction mixture was chilled and the crude dye collected on a filter and washed with methyl alcohol. After recrystallization from a mixture of pyridine and methyl alcohol, 1.4 g. (64%) of pure dye was obtained as purplish needles, M.P. 227-228" dec.

Example 23.-1,1',3,3 -tetraphenylimidazo [4,5 -b] quinoxalinocarbocyanine p-toluenesulfonate A mixture of 5.1 g. (2 mols.) of 2-methyl-1,3-diphenylimidazo [4,5-b]quinoxa liniurn p-toluenesulfonate, 1.6 g. (1 mo1.+100% excess) of diethoxymethyl acetate, and 15 ml. of pyridine was refluxed ten minutes. The reaction mixture was chilled and the crude dye collected on a filter and washed with water and then with acetone. After recrystallization from methyl alcohol, 1.9 g. (44%) of pure dye was obtained as bluish crystals with a shiny reflex, M.P. 286288 dec.

Analysis.-Calcd. for C H N O S: C, 73.02; H, 4.48. Found: C, 73.2; H, 4.5.

Example 24.-3'-ethyl-1,3-diphenylimidazo [4,5-b] quinoxalinothiacyanine iodide A mixture of 2.6 g. (1 mol.) of 2-methyl-1,3-diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 2 g. (1 mol.) of 3-ethyl-2-phenylmercaptobenzothiazolium iodide, 15 ml. of ethyl alcohol, and 0.5 g. (1 mol.) of triethylamine was refluxed for 15 minutes. The reaction mixture was chilled and the crude dye collected on a filter and washed with water and then with acetone. After recrystallization from methyl alcohol, 0.7 g. (23%) of pure dye was obtained as yellow plates, M.P. 288289 dec.

Example 25 .-3 '-ethyl- 1,3-diphenylimidazo [4,5 -b] quinoxalino-oxacarbocyanine iodide iodide, 15 ml. of ethyl alcohol, and 0.5 g. 1 mol.) of 7 triethylamine was refluxed 15 minutes. The reaction mixture was chilled and the crude dye collected on a filter and washed with water and then with acetone. After recrystallization from methyl alcohol, 0.6 g. (19%) of pure dye was obtained as green crystals with a shiny reflex, M.P. 289-290 dec.

Example 26.3-ethyl-1,3-diphenylimidazo [4,5-b] quinoxalinothiacarbocyanine iodide A mixture of 2.6 g. (1 mol.) of 2-methyl-l,3-diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 2.25 g. (1 mol.) of Z-B-acetanilidovinyl-3-ethylbenzothiazolium iodide, 15 ml. of ethyl alcohol, and 0.5 g. (1 mol.) of triethylamine was refluxed 15 minutes. The reaction mixture was chilled and the crude dye was collected on a filter and washed with water and then with acetone. After recrystallization from methyl alcohol, 1.0 g. (30%) of pure dye was obtained as dark green crystals, M.P. 288289 dec.

Example 27.-l',3',3-trimethyll,3-diphenylimidazo [4,S-b]quinoxalinoindocarbocyanine iodide N (1.1 o a C aHb Example 28.-1'ethy1-1,3-diphenylimidazo[4,5-b] quinoxalino-2'-carbocyanine iodide CH: CH;

A mixture of 2.6 g. (1 mol.) of 2-methyl-1,3-diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 2 g. (1 mol.) of 2 8-anilinovinyl-Z-ethylquinolinium iodide, 10 ml. of acetic anhydride, and l g. (2 mols.) of triethylamine was stirred at room temperature for two hours. The reaction mixture was chilled and then filtered. The filtrate was treated with 500 ml. of ether and the oily layer separated from the supernatant liquid by decantation and then washed first with ether and then with water. The oily layer was treated with acetone and the mixture chilled. The crude dye was collected on a filter and washed with acetone. After recrystallization from pyridine, 0.3 g. (9%) of pure dye was obtained as green crystals with a shiny reflex, M.P. 284-285 dec.

Example 29.-2-p-dimethylaminostyryl-1,3-diphenylimidazo [4,5 -b] quinoxalinium p-toluenesulfonate A mixture of 2.6 g. (1 mol.) of 2-methyl-1,3-diphenylimidazo[4,5b]quinoxalinium p-toluenesulfonate, l g. (1 mol. +33% excess) of p-dimethylaminobenzaldehyde and 15 ml. of acetic anhydride was refluxed ten minutes. The reaction mixture was chilled and the crude dye collected on a filter and washed with acetone. After recrystallization from ethyl alcohol, 0.65 g. of pure dye was obtained as deep red crystals, M.P. 250-251 dec.

Example 30.5-[ 1,3-diphenylimidazo [4,5-b] quinoxalin- 2( 3H) -ylidene) ethylidene] -3-ethylrhodaniue of a number of intermediate compounds that are employed in above Examples 12 to of the invention.

Example 31.--2,3-di- (2 hydroxyethylamino)quinoxaline N g Imromomon Nnornomon 2,3-dichloroquinoxaline (25 g., 1 mol.) was added in portions to 31 g. (4 mols.) of Z-hydroxyethylamiue with shaking. After A of the addition was complete, the temperature rose and the addition was completed with cooling. The reaction mixture was heated on a steam bath for four hours. The reaction mixture was stirred with water and the product collected on a filter and washed with water. A yield of 31 g. (100%) of colorless crystals was obtained, M.P. 180-482".

Analysis.Calcd. as C I-I N O C, 58.04; H, 6.50; N, 22.58. Found: C, 57.7; H, 6.7; N, 22.8.

Example 32.1,3-di(Z-hydroxyethyl)-2-methylimidazo [4,5-b] quinoxalinium p-toluenesulfonate H0 CH CHg I /N N O I c-cm W HO CHzCHa OaSC7H A mixture of 31.1 g. (1 mol.) of 2,3-di(2-hydroxyethylamino)quinoxaline, 19 g. (1 mol.) of p-toluene sulfonic acid, and 100 ml. of triethylorthoacetate was slowly distilled over a period of 1 /2 hours. The temperature of the vapors remained at 73. The residue was washed several times with ether and used without further purification.

Example 3 3 .2, 3-di(allylamino)quinoxa1ine I \N NOHzCH=CH| 2,3-dichloroquinoxaline (20 g., 1 mol.) was added in small portions to 34.2 g. (4 mols.+50% excess) of allylamine with stirring maintaining a temperature below 45 by means of a water bath at 20". After the addition was complete, the mixture was stirred in the water bath for 40 minutes. The mixture was then heated on a steam bath for three hours. The mixture was stirred with one 1. of water for 30 minutes and then collected on a filter and Washed with water. A yield of 24.2 g. of colorless product was obtained, M.P. 8688.

Example 34.-1,3-diallyl-2-methylimidazo[4,5-b]quinoxalinium p-toluenesulfonate ?Hr-CH=CH1 I \N N-0aSC7 1 CHg-CH=CH2 A mixture of 21.8 g. (1 mol.) of 2,3-di(allylamino)- quinoxaline, 17.1 g. (1 mol.) of p-toluenesulfonic acid, and ml. of acetic anhydride was refluxed 2% hours. The reaction mixture was chilled and treated with one 1. of ether. The oily layer was separated from the supernatant liquid by decantation and then washed with ether, until the oil became crystalline. The product was collected on a filter and washed with ether. A yield of 32.5 g. (82%) of colorless salt was obtained, M.P. 157-159 dec.

Analysis.Calcd. for C H J-I O S: C, 63.26; H, 5.54. Found: C, 63.1; H, 5.4.

Example 35 .2,3-dianilinoquinoxaline A mixture of 20 :g. (1 mol.) of 2,3-dichloroquinoxaline and 40 1g. (4 mols.) of aniline was fused on a steam bath and then heated for an additional hour. The reaction mixture was dissolved in 300 ml. of ethyl alcohol. Water was added in small portions until 50 ml. had been added, and the product collected on a filter and washed with water. A yield of 28 g. (93%) of colorless product was obtained, M.P. 73-80".

Example 36.2-methyl-l,3-diphenylimidazo[4,5-b]- quinoxalinium p-toluenesulfonate A mixture of 30 g. (1 mol.) of 2,3-dianilinoquinoxaline, 19 g. (1 mol.) of p-toluenesulfonic acid, and ml. of acetic anhydride was refluxed three hours. The reaction mixture was chilled and treated with 600 ml. ether. The oily layer was separated from the supernatant liquid by decantation and then washed twice more with ether. The oily residue was treated with 300 ml. of acetone and the solid collected on a filter and washed with acetone. A yield of 30 g. (60%) of cream colored crystals was obtained, M.P. 275-285 dec.

Analysis.-Calcd. for C 'H N4O 'S: C, 68.45; H, 4.76; N, 11.02. Found: C, 68.4; H, 5.0; N, 10.9.

Examples 37 through 64 illustrate further useful cyanine dyes featuring an imidazo[4,5-b]quinoxaline nucleus. Note that both nuclei of Examples 37, 39, 40, 4244, 47, 48, 53, 55, 56, 58-60, 62, and 63 are desensitizing nuclei. In the formula Ph represents phenyl and Me represents methyl.

Example 37 .-6,6' dichloro-l,1',3,3-tetraphenylimidazo [4,5-b]quinoxalinocarbocyanine p-toluenesulfonate A mixture of 5.4 g. (2 mols.) of 6-chloro-2-methyl- 1,3-diphenylirnidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1.6 g. (1 mol.+100% excess) of diethoxymethyl acetate and 10 ml. of pyridine was refluxed ten minutes. After chilling, the solid was collected on a filter, and washed with acetone. After recrystallization from methyl alcohol, 1.5 g., (33%) of pure dye was obtained as purple crystals with a green reflex, M.P. 29 3-294 dec.

Example 38.-6-chloro-1',3',3',-trirnethyl-1,3-diphenylimidazo [4,5 -b] quinoxalinoindocarbocyanine iodide A mixture of 2.7 g. (1 mol.) of 6-chloro-2-methyl-1,3- diphenylimidazo [4,5-b] quinoxalinium p-toluenesulfonate, 2.2 g. (1 mol.) of 2-(Z-acetanilidovinyl-1,3,3-trimethyl- 3H-indolium iodide, 10 ml. of ethyl alcohol, and 0.5 g. (1 mol.) of triethylamine was refluxed 30 minutes. After chilling, the crude dye was collected on a filter and suspended in benzene. The dye was collected on a filter and washed with benzene. After recrystallization from methyl alcohol, 0.5 g. (14%) of pure dye was obtained as green crystals, M.P. 283284 dec.

Example 39.6-chloro-2- 1-methyl-2-phenyl-3-indolyl) vinyl] 1,3 diphenylimidazo[4,5-b]quinoxalinium ptoluenesulfonate A mixture of 1.35 g. (1 mol.) of 6-chloro-2-methyl-1,3- diphenylimidazo [4,5-b] quinoxalinium p-toluenesulfonate, 0.6 g. (1 mol.) of 1methyl-2-phenylindole-3-carboxaldehyde, and 10 ml. of acetic anhydride was refluxed ten minutes. After chilling, the crude dye was collected on a filter, washed with acetic anhydride and then with acetone. After recrystallization from ethyl alcohol, 0.5 g. of pure dye was obtained as red crystals with a shiny reflex, M.P. 288289 dec.

18 Example 40.6-chloro 2-[2-(9-methyl 3 carbazolyl)- vinyl] 1,3 diphenylimidazo[4,5-b] quinoxalinium ptoluenesulfonate Example 4l.6 chloro-2-p-dimethylaminostyryl-1,3-diphenylimidazo[4,S-b]quinoxalinium p-toluenesulfonate A mixture of 2.7 g. (1 mol.) of 6-chloro-2-methy1- 1,3 diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate 1 g. (1 mo1.;+30% excess) of p-dimethylamino- 1 benzaldehyde, and 10 ml. of acetic anhydride was refluxed for 20 minutes. After chilling, the crude dye was collected on a filter, washed with acetic anhydride and then with acetone. After recrystallization from ethyl alcohol, 2.0 g. (59%) of pure dye was obtained as dark crystals, M.P. 280-281 dec.

Example 42.1,3 diallyl 6 chloro Z[2 (1 methyl 2 phenyl 3 indolyl)vinyl]imidaz0[4,5 b] quinoxalinium p-toluenesulfonate airport-( 1H1 N osogmm & NMe

CHn=CH-CH2 Ph A mixture of 2.3 g. (1 mol.) of 1,3-diallyl-6-ch1oro-2- methylimidazo [4,5 -b]quinoxaliniurn p toluenesulfonate, 1.2 g. (1 mol.) of 1-methyl-2-phenylindole-3-carboxalde hyde, and 10 ml. of acetic anhydride was refluxed ten minutes. After chilling, the reaction mixture was treated with ether and the crude dye which separated was collected on a filter and washed with ether. After recrystallization from ethyl alcohol, 2.2 g. (65%) of pure dye was obtained as red needles, M.P. 24024l dec.

Analysis.-Calcd. for C H ClN O S: C, 68.0; H, 5.0; N, 10.2 Found: C, 67.8; H, 4.9; N, 10.0.

Example 43.l,l,3,3 tetraallyl 6,6 dichloroimidazo [4,5 -b quinoxalinocarbocy-anine p-toluenesulfonate A mixture of 4.7 g. (2 mols.) of 1,3-diallyl-6-chloro- 2-methylimidazo [4,5-b] quinoxalinium p-toluenesulfonate, 1.6 g. (1 ml.+100% excess) of diethoxymethyl acetate and 20 ml. of pyridine was refluxed 20 minutes. After chilling, the crude dye was collected on a filter and washed with acetone. After recrystallization from methyl alcohol, 3.1 g. (79%) of pure dye was obtained as green crystals with a golden reflex, M.P. 251-252 dec.

Example 44.6,6,7,7' tetrachloro 1,1',3,3' tetraphenylimidazo[4,5 b] quinoxalinocarbocyanine ptoluenesulfonate A mixture of 5.8 g. (2 mols.) of 6,7-dichloro-2-methyl- 1,3 diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate 1.6 g. (l m0l.+100% excess) diethoxymethyl acetate and 30 ml. of pyridine was refluxed for ten minutes. After chilling, the crude dye was collected on a filter and washed with acetone. After recrystallization from methyl alcohol, 1.2 g. (24%) of pure dye was obtained as green prisms with a golden reflex, M.P. 3l2 313 dec.

Example 45.6,7 dichloro 1',3',3' trimethyl 1,3- diphenylimidazo[4,5 b]quinoxaline indocarbocyanide iodide A mixture of 2.7 g. (1 mol.) of 6,7-dichloro-2-methyl- 1,3-diphenylimidazo[4,5b]quinoxalinium iodide, 2.3 g. (1 mol.) of 2 (2 acetanilidovinyl) 1,3,3 trimethyl- 3H-indolium iodide, 20 ml. of acetic anhydride and 0.5 g. (1 mol.) of triethylamine was refluxed 20 minutes. After chilling, the crude dye was collected on a filter, washed with acetic anhydride and then with acetone. After recrystallization from methyl alcohol, 1.5 g. (42%) of pure dye was obtained as purplish crystals, M.P. 310-31l dec.

Example 46.-6,7 dichloro 1' ethyl 1,3 diphenylimidazo[4,5 b]quin0xalino 2' carbocyanine ptoluenesulfon'ate A mixture of 2.9 g. (1 mol.) of 6,7-dichloro-2-methyL 1,3 diphenylimidaz0[4,5-'b]quinoxalinium p toluenes-ulfonate, 2.3 g. (1 mol.) of 2-(2-acetanilidovinyl)-1-ethylquinolinium p-toluenesulfonate, and 30 ml. of acetic anhydride was stirred at room temperature for two hours and at 55-60 for 3 hours. After chilling, the mixture was filtered and the solid washed with acetic anhydride and then with acetone. The filtrates were combined and treated with ether. The solid was collected on a filter and washed with ether and then with acetone. After recrystallization from ethyl alcohol, 0.5 g. (13%) of pure dye was obtained as dark crystals with a golden reflex, M.P. 185187 dec.

20 Example 47.6,7 dichloro 2[2 (9 methyl 3 carbazoyl)vinyl] 1,3 diphenylimidazo[4,5 b]quinoxalinium p-toluenesulfonate ik/ C-CH=CH C1 \N l I oso201111 10 l N A mixture of 2.9 g. (1 mol.) of 6,7-dichloro-2-methyl- 1,3 diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1.1 g. (1 mol.) of 9-methylcarbazole-3-carboxaldehyde, and 20 ml. of acetic anhydride was refluxed 15 minutes. After chilling, the crude dye was collected on a filter, washed with acetic anhydride and then with acetone. After recrystallization from methyl alcohol, 0.6 g. (16%) of pure dye was obtained as dark red crystals, M.P. 312-313 dec.

Example 48.-6,7 dichloro 2 [2 (l ethyl 2- phenyl 3 indolyl)vinyl] 1,3 diphenylimidazo [4,5-b] quinoxaliniurn p-toluenesulfonate 1| n N C1 T CCH=CH NMe 01 \N Ph N 080207111 CCH=CH- -NMe| I Q N osoicqm A mixture of 2.9 g. (1 mol.) of 6,7-dich1oro-1,3-diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1 g. (1 mol. plus 30% excess) of p-dimethylaminobenzaldehyde and 20 ml. of acetic anhydride was refluxed 15 minutes. After chilling, the crude dye was collected on a filter and washed with acetic anhydride and then with acetone. After recrystallization from methyl alcohol, 1.2 g. (34%) of pure dye was obtained as green crystals with a red reflex, M.P. 293-294 dec.

Example 50.-4-[(6,7 dichloro 1,3 diphenylimidazo [4,5 -b] quinoxalin-2 3H -ylidene) ethylidene] -3-phenyl-2-isoxazolin-5-one 1| n N co-o f It p C=CHCH=C\ C1 1=N Ph Ph A mixture of 5.3 g. (1 mol.) of 6,7-dichloro-2-methyll,3-diphenylimidazo[4,5-b]quinoxalinium iodide, 2.7 g.

A mixture of 1.45 g. (1 mol.) of 4-[(6,7-dichloro-l,3- diphenylimidazo[4,5-b]quinoxalin 2(3H) ylidene)ethylidene]-3-phenyl-2-isoxazolin-S-one and 5 g. of dimethylsulfate was heated over a free flame with stirring. After the solid dissolved, the mixture was refluxed for one minute. After cooling, ml. of acetone were added and the mixture chilled. The dye was collected on a filter and washed very thoroughly with acetone. A 51% yield of a brownish powder was obtained, M.P. 274-275 dec.

Example 52.Anhydro-6,7-dichloro-2-{2-[5-oxo-3-phen yl-2-(3-sulfopropyl)-3-isoxazolin 4 yl]}vinyl-l,3-diphenylimidazo [4,5-b] quinoxalinium hydroxide A mixture of 1.45 g. (1 mol.) of 4-[(6,7-dichloro-l,3- diphenylimidazo[4,5-b]quinoxalin-2(3H) ylidene)ethylidene-3-phenyl-2-isoxazolin-5-one and 6 g. propane sultone was heated to around 180 when all the material goes into solution. The mixture was heated at 180200 for two minutes. After cooling, 125 ml. of acetone was added and the mixture was chilled. After chilling overnight, the dye was collected on a filter and washed thoroughly with acetone. A yield of an orange powder was obtained, M.P. 247-250" dec. pyridine and precipitating with methyl alcohol. A 79% yield of pure dye was obtained as dark brown crystals, M.P. 320.

Example 53.-8,8',10,10' tetraphenyl-SH-berizo[f]irnidazo [4,5 -b] quinoxalino-carbocyanine bromide A mixture of 5. 6 g. (2 mols.) of 9-methyl-8,10-dipheuyl-8H benzo[f]imidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1.6 g. (1 mol. 100% of excess) of diethoxymethyl acetate and 10 ml. of pyridine was refluxed 15 minutes. After chilling, the mixture was treated with ether and the solid which separated was collected on a filter and washed with ether. The crude dye was extracted with 250 ml. of methyl alcohol and the solution concentrated to ml. After chilling, the mixture was filtered and the solid Washed lightly with methyl alcohol and then discarded. The filtrate was treated with an aqueous solution of sodium bromide. After chilling, the dye was collected on a filter and washed with water. After recrystallization from methyl alcohol, 1.6 g. (37%) of pure dye was obtained as dark purplish crystals, M.P. 305- 307 dec.

Example 54.-l',3,3-trimethyl-8,l0-diphenyl 8H-benzo [f]imidazo[4,5-b]quinoxalino-indocarbocyanine iodide A mixture of 2.8 g. 1 mol.) of 9-methyl8,10-diphenylbenzo[f]imidazo [4,5-b1quinoxalinium p-toluenesulfonate, 2.2 g. (1 mol.) of 2-(2-acetanilidoviny1)-l,3,3-trimethylindolium iodide, 10 ml. of acetic anhydride and 0.5 g. (1 mol.) of triethylamine was refluxed ten minutes. After chilling, the crude dye was collected on a filter, washed with acetic anhydride and then with ether. After recrystallization from methyl alcohol, 1.1 g. (31%) of pure dye was obtained as green crystals with a bright reflex, M.P. 320321 dec.

Example 55.9-[2-(9-methyl 3 carbazolyl)vinyl]-8,10-

diphenyl 8Hbenzo[f]imidazo[4,5-b]quinoxalinium ptoluenesulfonate A mixture of 2.8 g. (1 mol.) of 9-methyl-8,l0-diphenyl 8H benzo [f]imidazo[4,5-b1quinoxaliniurn p-toluenesulfonate, 1.1 g. (1 mol.) of 9-methylcarbazole-3-carboxaldehyde and 10 ml. of acetic anhydride was refluxed 15 minutes. After chilling, the reaction mixture was treated with ether and the crude dye collected on a filter and washed with ether. After recrystallization from methyl alcohol, 0. 6 g. (16%) of pure dye was obtained as dark crystals, M.P. 215-218 dec.

Example 5 6.9- [2-( l-methyl-2-phenyl-3 indolyl)vinyl] 8,10-diphenyl SH-benzo [f] imidazo 4,5-b quinoxalinium bromide A mixture of 2.8 g 1 mol.) of 9-methyl-8,10-diphenyl- 8H benzo[f]imidazo[4,5-b] quinoxalinium p-toluenesulfonate, 1.2 g. (1 mol.) of 1-methyl-2-phenylindole-3-carboxaldehyde and 10 ml. of acetic anhydride was refluxed 15 minutes. After chilling, the reaction mixture was treated with ether and the crude dye which separated was collected on a filter and washed with ether. The crude dye was dissolved in ethyl alcohol and treated with an aqueous solution of sodium bromide. After chilling, the dye was collected on a filter and washed with water. After recrystallization from methyl alcohol, 0.7 g. (21%) of pure dye was obtained as dark crystals, M.P. 310 dec.

23 Example 57.9-p-dimethylaminostyryl-8,IO-diphenyl- SH-benzo [f 1 imidazo [4,5-b] quinoxalinium bromide A mixture of 2.8 g. (1 mol.) of 9-methyl-8,10-diphenyl- 8H benzo[f]imidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1 g. (1 ml.+33% excess) of p-dimethylaminobenzaldehyde and 10 ml. of acetic anhydride was refluxed minutes. After chilling, the crude dye was collected on a filter and washed with acetic anhydride and then acetone. The crude dye was dissolved in ethyl alcohol and the solution treated with an aqueous solution of sodium bromide. After chilling, the dye was collected on a filter and Washed with water and then acetone. After rcerystallization from ethyl alcohol, 0.7 g. (28%) of pure dye was obtained as green crystals, M.P. 262-263 dec.

Example 58.6,6'-dinitro-1,1,3,3'-tetraphenylimidazo- [4,5-b1quinoxalino p-toluenesulfonate A mixture of 5.5 g. (2 mols.) of 2-methyl-6-nitro-1,3- diphenylimidazo [4,5 -b] quinoxalinium p-toluenesulfonate, 10 ml. of pyridine and 1.6 g. (1 mol.+l00% excess) of diethoxymethyl acetate was refluxed seconds. After chilling, the crude dye was collected on a filter, washed well with acetone and dried. After recrystallization from methyl alcohol, 2.2 g. (47%) of pure dye was obtained as green crystals, M.P. 206-207 dec.

Example 59.-l,3-dially1-6'-nitro-1',3-diphenylimidazo- [4,5-b]quinoxa1ino carbocyanine p-toluenesulfonate Example 60.-3'-ethyl-6,6'-dinitro-1,3-diphenylimidazo- [4,5-b]quinoxalinothiacarbocyanine p-toluenesulfonate 1:11 N N s OzN N02 /CCH=CH-CH=O\ \N/ K 68 2 11311 N 1 Et Ph A mixture of 2.8 g. (1 mol.) of 2-methyl-6nitro-1,3- diphenylimidazo[4,5-b1quinoxalinium p-toluenesulfonate,

1.25 g. (1 mol.) of 3-ethyl-2-formylmethylene-G-nitrobenzothiazoline and 20 m1. of acetic anhydride was refluxed 5 minutes. After chilling, the crude dye was collected on a filter and washed first with acetic anhydride and then with acetone. After recrystallization from methyl alcohol, 2.2 g. (57%) of pure dye was obtained as green crystals with a bright reflex, M.P. 250-252" dec.

Example 6l.1,3',3'-trimethyl-6-nitro-1,3-diphenylimidazo [4,5 -b] quinoxalino-indocarbocyanine iodide A mixture of 2.8 g. (1 mol.) of 2-methyl-6-nitro-1,3- diphenylimidazo [4,5-b] quinoxalinium p-toluenesulfonate, 2.2 g. (1 mol.) of 2-(2-acetanilidovinyl)-1,3,3-trimethyl- 3H-indolium iodide, 20 ml. of acetic anhydride and 0.5 g. (1 mol.) of triethylarnine was refluxed three minutes. After chilling, the crude dye was collected on a filter and washed with acetone. After recrystallization from methyl alcohol, 1.1 g. (31%) of pure dye was obtained as dark crytsals with a shiny reflex, M.P. 285-286 dec.

Example 62.2 [2 (9-methyl-3-carbazolyl)vinyl1-6- nitro 1,3 diphenylimidazo[4,5-b1quinoxalinium ptoluenesulfonate A mixture of 2.8 g. (1 mol.) of 2-methyl-6-nitro-1,3- diphenylimidazo[4,5-b1quinoxa1inium p-toluenesulfonate, 1.1 g. (1 mol.) of 9-methylcarbazole-3-carboxaldehyde and 20 ml. of acetic anhydride was refluxed three minutes. After chilling, the crude dye was collected on a filter and washed first with acetic anhydride and then with acetone. After recrystallization from methyl alcohol, 1.8 g. (42%) of pure dye was obtained as dark reddish crystals, M.P. 291-292 dec.

Example 63.2-[2-(1-methy1-2-phenyl-3-indolyl)vinyl]- 6 nitro 1,3 diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate A mixture of 2.8 g. (1 mol.) of 2-methyl-6-nitro-1,3- diphenylimidazo[4,5-b]quinoxalinium p-toluenesulfonate, 1.2 g. (1 mol.) of 1-methyl-2-phenylindole-3-carboxaldehyde and 20 ml. of aceitc anhydride was refluxed three minutes. After chilling, the crude dye was collected on a filter and washed first with acetic anhydride and then with acetone. After recrystallization from ethyl alcohol, 1.9 g. (49%) of pure dye was obtained as dark crystals with a shiny reflex, M.P. 303304 dec.

Example 64.-2-p-dimethylaminostyryl-6-nitro-1,3-diphenylimidazo 4,5 -b] quinoxalinium p-tolenesulfonate A mixture of 2.8 g. (1 mol.) of 2-methyl-6-nitro-1,3- diphenylimidazo[4,5-b1quinoxalinium p-toluenesulfonate, 1 g. (1 mol.+33% excess) of p-dimethylaminobenzaldehyde and 20 ml. of acetic anhydride was refluxed five minutes. After chilling, the crude dye was collected on a filter and washed, first with acetic anhydride and then with acetone. After recrystallization from methyl alcohol, 2.0 g. (55%) of pure dye was obtained as dark crystals with a coppery reflex, M.P. 257-258 dec.

Intermediates useful in preparing the dyes of Examples 37 through 64 are shown in Examples 65 through 74, below.

Example 65 .-6-chloro-2,3-dihydroxyquinoxaline N// OH A mixture of 71.5 g. (1 mol) of 4-chloro-o-phenylenediamine and 675 ml. of ethyl oxalate was refluxed one hour and then the alcohol formed allowed to distill over slowly. After all of the alcohol had distilled, the reaction mixture was chilled and the solid collected on a filter. The solid was suspended in 800 ml. of methyl alcohol and then collected on a filter. The solid was again suspended in 800 ml. of methyl alcohol and collected on a filter. A yield of 86 g. (88%) of finely divided solid was obtained, M.P. 300".

Example 66.2,3,6-trichloroquinoxaline N Cl o1 To a suspension of 98 g. (1 mol) of 6-chloro-2,3-dihydroxyquinoxaline in 200 ml. of phosphoryl chloride, was added 208 g. (2 mols) of phosphorus pentachloride. The mixture was heated until the internal temperature was 80 whereupon a vigorous evolution of hydrogen chloride took place. When the reaction slowed, the temperature was slowly raised to 118 over a period of one hour. The phosphoryl chloride was allowed to distill and about 275 ml. collected. The residue was poured into 2 l. of ice and water with stirring. The mixture was neutralized with a solution of sodium carbonate and the solid collected on a filter. The solid was extracted with 600 ml. of boiling benzene, separating the benzene from the water layer before cooling. On chilling, 80.5 g. (69%) of gray crystals were obtained, M.P. 143-144". A second crop of 27 g, (23%) was obtained from the benzene filtrate, M.P. 143-144". I

Example 67.6 chloro 2 methyl 1,3 diphenylimidazo [4,5-b] quinoxalinium-p-toluenesulfonate llh N N C] K/ I /C-CI'I3 \NAIF OSOzC1H1 A mixture of 23.4 g. (1 mol.) of 2,3,6-trichloroquinoxaline and 40 g. (4 mols.) of aniline was heated 30 minutes on a steam bath when all the material dissolved.

After heating for an additional 1% hours, the mixture was stirred with 400' ml. of water and the solid collected on a filter. The solid was dissolved in 250 ml. of ethyl alcohol, cooled and filtered and the filtrate treated with water. The heavy oil was separated from the water by decantation and then dissolved in 300 ml. of ether. The solution was dried and the ether removed. The residue was dissolved in ml. of acetic anhydride and 19 g. (1 mol.) of p-toluenesulfonic acid and the solution refluxed 1% hours. After chilling, the mixture was treated with 2 l. of ether and the oil which separated washed with additional ether. The oil was stirred with 150 ml. of acetone and the material becomes crystalline. After chilling, the solid was collected on a filter and washed with acetone. A yield of 37 g. (68%) of gray crystals was obtained, M.P. 278-280 dec.

Analysis.--Calcd for C H ClN O S: C, 64.1; H, 4.3. Found: C, 64.4; H, 4.3.

C-GH:

To 34.2 g. (4 mols. +50% excess of allylamine was added 23.4 g. (1 mol.) of 2,3,6-trichloroquinoxaline in small portions with shaking. After the addition was complete, the mixture was heated on a steam bath for two hours. The reaction mixture was stirred with 200 ml. of water and the water layer decanted. The oil was dissolved in 400 ml. of benzene and the benzene solution washed with water. After removing the benzene, the residue was dissolved in 150 ml. of acetic anhydride and 19 g. (1 mol.) of p-toluenesulfonic acid, and the mixture refluxed two hours. After chilling, the mixture was stirred twice with 2 l. of ether. The residue was stirred with 150 m1. of acetone and the solution chilled. After chilling, 14.4 g. (33%) of colorless crystals were obtained, M.P. 173- 175 dec.

Analysis.-Calcd for C H CIN O S: C, 58.6; H, 4.9; N, 11.9. Found: C, 58.9; H, 4.9; N, 12.0.

Example 69.6,7-dichloro-2,3-dihydroxyquinoxaline Example 70.2,3,6,7-tetrachloroquinoxaline o1- -o1 A mixture of 57.6 g. (1 mol.) of 6,7-dichloro-2,3- dihydroxyquinoxaline, 140ml. of phosphoryl chloride and 104 g. (2 mols.) of phosphorus pentachloride was refluxed for four hours. After chilling, the solid was collected on a filter and then suspended in 500 ml. of ice and water, collected on a filter and washed with water. A yield of 51.1 g. (76%) of light tan powder was obtained, M.P. -171.

27 Example 7l.2,3-dianilino-6,7-dichloroquinoxaline N Cl NPHh Cl NH Ph A mixture of 51.1 g. (1 mol.) of 2,3,6,7-tetrachloroquinoxaline and 79 ml. (4 mols.) of aniline was heated on a steam bath for two hours. The solid was ground in a mortar and then boiled with lfitl ml. of methyl alcohol. After chilling, the solid was collected on a filter, washed with methyl alcohol, then stirred with 400 ml. of water, collected on a filter and washed with water. A yield of 66.3 g. (91%) of a tan solid was obtained, M.P. 195- 200.

Example 72.6,7 dichloro 2 methyl 1,3 diphenylimidazo [4,5 -b] quinoxalinum-p-toluenesulfonate A mixture of 66.3 g. (1 mol.) of 2,3-dianilino-6,7-dichloroquinoxaline, 280 ml. of acetic anhydride and 33 g. (1 mol.) of p-toluenesulfonic acid was refluxed 1% hours. The reaction mixture was cooled and treated with 2 /2 1. of ether. The ether was decanted from an oil which was washed five times more with 150 ml. portions of ether. The residue was stirred with 100 ml. of pyridine, and the very finely divided product collected on a filter. The solid was washed well with acetone. A yield of 47 g. (47%) of yellow powder was obtained, M.P. 210- 245 Example 73 .-2,3-dihydroxybenzo[f] quinoaxiline A mixture of 100 g. (1 mol.) of 1,2-naphthalenediamine and 1 kg. of ethyl oxalate was refluxed for 30 minutes and then the alcohol formed allowed to distill slowly over a period of two hours. After chilling, the solid was collected on a filter. The solid was suspended in 600 ml. of methyl alcohol, and then collected on a filter. After repeating this washing, a yield of 112 g. (83%) of brown solid was obtained, M.P. 320".

Example 74.-2,3-dichlorobenzo [f] quinoxaline I TC1 N C1 A mixture of 42.4 g. (1 mol.) of 2,3-dihydroxybenzo- [f]quinoxaline, 200 ml. of phosphoryl chloride and 83.2 g. (2 mols.) of phosphorus pentachloride was refluxed three hours. After chilling, the solid was collected on a filler and then stirred with ice and water and collected on a filter again. The filtrate was poured into 1 1. of ice and water and the solid collected on a filter. The solids were combined, 48.8 g. (97%) and used without further purification.

28 Example 75.--9-methyl-8,IO-diphenyl 8H benz[f]imidazo [4,5-b quinoxalinium p-toluenesulfonate A mixture of 48.8 g. (1 mol.) of 2,3-dichlorobenzo- [fJquinoxaline and ml. of aniline was refluxed 2% hours. After chilling, the reaction mixture was washed three times with petroleum ether. The residue was treated with 450 ml. of methyl alcohol. After chilling, 30 g. of solid was collected on a filter. The filtrate was concentrated to dryness and the residue steam distilled until no more aniline was obtained. The oil which remained solidified on cooling. The solidified oil was dissolved in 150 ml. of acetic anhydride and 18 g. p-toluenesulfonic acid and the mixture refluxed two hours. After chilling, the mixture was filtered to remove unreactive solid. The filtrate was treated with 2 l. of ether and the oil which separated washed with ether. The residual oil was dissolved in ethyl alcohol and the solution chilled and filtered. The solid which was collected on a filter was unreactive. The filtrate was treated with ether, and the oil stirred several times with fresh ether until crystalline. The solid was collected on a filter. A yield of 36.5 g. (48%) of brown solid was obtained from which dyes could be obtained.

Example 76.-2,3-dihydroxy-6-nitroquinoxaline N OzN Example 77.2,3-dichloro-6-nitroquinoxaline N OzN or A mixture of 38.2 g. (1 mol.) of 2,3-dihydroxy-6-nitroquinoxaline and 200 ml. of phosphoryl chloride and 83.2 g. (2 mols.) of phosphorus pentachloride was refluxed 1% hours. After chilling, the solid was collected on a filter and then suspended in 500 ml. of ice and water and filtered again. A yield of 24.5 g. (50%) of tan solid was obtained, M.P. 252-253 dec.

Example 7 8.--2-methyl-6-nitro 1,3 diphenylimidazo [4, 5-b] quinoxalinium p-toluenesulfonate N OzN C-CH;

A mixture of 24.5 g. (1 mol.) of 2,3-dichloro-6-nitroquinoxaline and 37.2 g. (4 mols.) of aniline was heated two hours on a steam bath. To the cooled reaction mixture was added 200 ml. of acetic anhydride and 19 g. (1 mol.) of p-toluenesulfonic acid and the mixture refluxed l /z hours. After chilling, the mixture was treated with two liters of ether and the separated oil washed with ether. The solid which formed was collected on a filter and then suspended in acetone and collected on a filter again. A yield of 42.5 g. (77%) of tan crystals was obtained, M.P. 284-285 dec.

Analysis.-Calcd. for C29H23N505SI C, H, N, 12.6. Found: C, 62.8; H, 4.1; N, 12.7.

The cyanine dyes containing a substituted imidazo- [4,5-b1quinoxaline nucleus, such as those of Examples 37-64, are highly useful spectrally sensitizing electron acceptors in direct positive emulsions. Dyes containing a nitro, chloro or dichloro substituted imidazo[4,5-b] quinoxaline nucleus are especially useful in direct positive emulsions. The chloro (e.g., monochloro and dichloro) substituted dyes are preferred. Such dyes are characterized by especially sharp adsorption peaks. Direct positive emulsions containing them have enhanced speed.

For the preparation of photographic emulsions, the new dyes of the invention are advantageously incorporated in the finished silver halide emulsion and should, of course, be uniformly distributed throughout the emulsion. The methods of incorporating dyes in emulsions are relatively simple and well known to those skilled in the art of emulsion making. For example, it is convenient to add the dyes from solutions in appropriate solvents, in which the solvent selected should have no deleterious eifect on the ultimate light-sensitive materials. Methanol, isopropanol, pyridine, etc., alone or in combination have proven satisfactory as solvents for the majority of our new dyes. The type of silver halide emulsions that are desensitized with our dyes include any of those prepared with hydrophilic colloids that are known to be satisfactory for dispersing light-sensitive silver halides, for example, emulsions prepared with hydrophilic colloids, such as, natural materials, e.g., gelatin, albumin, agar-agar, gum arabic, alginic acid, etc., and synthetic hydrophilic resins, e.g., polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, etc.

The concentration of our new dyes in the emulsion can be widely varied, i.e., generally from about to about 200 mg. per mole of silver halide. The specific concentration will vary according to the type of lightsensitive material in the emulsion and according to the effects desired. The most advantageous dye concentration for any given emulsion can be readily determined by making the tests and observations customarily used in the art of emulsion making. Our emulsions are coated to advantage on any of the support materials used for photographic elements, for example, paper, glass, cellulose derivatives, such as cellulose acetate, cellulose acetate-propionate, cellulose nitrate, etc., synthetic resins, such as polystyrene, polyethylene terephthalate and other polyesters, polyamides, such as nylon, and the like.

To prepare a gelatino-silver halide emulsion desensitized with one of our new dyes, the following procedure is satisfactory: A quantity of the dye is dissolved in a suitable solvent, and a volume of this solution containing the desired amount of dye is slowly added with intimate mixing to about 1,000 cc. of light sensitive gelatino-silver halide emulsion. With most of our dyes, from about 1 to 20 mg. of dye per liter of emulsion sufiices to produce the desired desensitizing eifect with the ordinary light-sensitive gelatino-silver bromide (including bromoiodide and chlorobromide) and fine-grain emulsions which include most of the ordinary employed light-sensitive gelatinosilver chloride emulsions. Somewhat smaller or even larger concentrations of dye may be necessary to secure the desired degree of desensitization. While the preceding has dealt with emulsions comprising gelatin, it will be understood that these remarks apply generally to any emulsions in which a part or all of the gelatin is substituted by another suitable hydrophilic colloid such as previously mentioned.

The above statements are only illustrative and are not to be understood as limiting our invention in any sense, as it will be apparent that our dyes can be incorporated by other methods in many of the emulsions customarily used in the art. For instance, in a less preferred method, the dyes can 'be incorporated by bathing a plate or film bearing an emulsion, in a solution of the dye.

Gur invention is still further illustrated by the following tabulation showing the relative speed data and percent desensitization produced in a gelatin-silver bromoiodide emulsion and in a gelatino-silver chlorobromide emulsion by representative dyes of our invention. The dyes, dissolved in suitable solvents, were added to separate portions of the emulsions at the concentrations indicated. After digestion at 50 C. for 10 minutes, the emulsions were coated on a cellulose acetate film support. A control coating was made of each emulsion containing no dye. A sample of each coatings was exposed with a sensitometer to a light source modulated with Wratten #35 and #38A filters. The exposed film strips were developed n a conventional developer having the formula:

Water to make 1 liter.

The developed strips were then fixed with a conventional fixing bath, washed and dried. From densitometric measurements the relative speeds were determined for each sample based on an arbitrary value of 100 for each of the two controls. The data obtained are tabulated below.

Dye of Dye con- Relative Percent example eentration Type oi emulsion speed desensiti- No. gJmole zation silver halide Silver bromoiodide 20 80 d 9 91 50 50 32 68 18 82 50 50 22 78 18 82 50 50 100 The silver bromoiodide emulsion contained 2 mole percent iodide and 98 mole percent bromide. The silver chlorobromide emulsion contained mole percent chloride and 20 mole percent bromide. From the data it can be seen that representative dyes of our invention desensitize up to 93% under the conditions used. Similarly it can be shown that other dyes of our invention are valuable desensitizers for photographic silver halide v emulsions. Although gelatino-silver halide emulsions were used for illustrative purposes, it is to be understood that our desensitizers are also used to advantage in emulsions in which gelatin is replaced by hydrophilic colloids mentioned previously as gelatin substitutes.

Our desensitizing dyes are employed to advantage in photographic elements where desensitization is required, for example, in making photographic silver halide emulsions used for the direct production of positive images, such as are described by Kendall et a1. U.S. Patent 2,541,472, issued Feb. 13, 1951, Kendall et al. U.S. Patent 2,669,515, issued Feb. 16, 1954, Hillson U.S. Patent 3,062,651, issued Nov. 6, 1962, British Patent 723,019, 1955, etc.

Solutions of Dyes 1, 3, 4, 5, 6, 7 and 8 were bleached by the developer solution described previously, indicating 31 that they have utility at bleachable filter dyes for photographic elements.

Our dyes are also used to advantage as biological stains.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A light-sensitive photographic silver halide emulsion containing a dye selected from those having one of the following formulas:

herein n represents a positive integer of from 1 to 4, m and g each represents a positive integer of from 1-2, d represents a positive integer of from 1 to 3, R and R each represents a member selected from the group consisting of an acyclic hydrocarbon substituent, an alkaryl substituent and an aryl substituent, R represents an alkyl group of from 1-12 carbon atoms, R and R each represents an alkyl group of from 1-6 carbons atoms, X represents an acid anion, Z represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, and Q represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring.

2. A light-sensitive photographic silver halide emulsion in accordance with claim 1 wherein the desensitizing dye is 1,1,3,3'-tetraethylimidazo[4,5-b]quinoxalinocarbocyanine chloride.

3. A light-sensitive photographic silver halide emulsion in accordance with claim 1 wherein the desensitizing dye is 1,3,3-triethylimidazo [4,5-b] quinoxalino-oxacarbocyanine iodide.

4. A light-sensitive photographic silver halide emulsion in accordance with claim 1 wherein the desensitizing dye is 1,3 ,3 '-triethylimidazo [4, 5 -b] quinoxalino-thia car-b ocyanine iodide.

5. A light-sensitive photographic silver halide emulsion in accordance with claim 1 wherein the desensitizing dye is 2 p dimethylaminostyryl-l,3-diethylimidazo[4,5-b]- quinoxalinium iodide.

6. A light-sensitive photographic silver halide emulsion in accordance with claim 1 wherein the desensitizing dye is 5-[ 1,3-diethylimidazo[4,5-b] quinoxalin-2-ylidene1-1,3- diethyl-Z-thiobarbituric acid.

7. A light-sensitive photographic element comprising a support having coated thereon at least one layer of the photographic emulsion of claim 1.

8. A light-sensitive photographic silver halide emulsion containing a cyanine dye salt which comprises two nuclei joined together by methine linkage, at least one of said nuclei being an imidazo (4,5-b)quinoxaline nucleus, said nucleus being joined through the Z-carbon atom thereof to said methine linkage, and a second nucleus to complete said cyanine dye.

9. A light-sensitive photographic silver halide emulsion in accordance with claim 8 wherein said second nucleus contains a heterocyclic nitrogen atom, and the methine linkage is part of a polyene chain containing an equal number of alternating single and double bonds, one terminal carbon atom of said chain being the 2-carbon atom of an imidazo(4,5-b)quinoxaline nucleus, the other terminal carbon atom of said chain being in said second nucleus and attached to said heterocyclic nitrogen atom.

10. A light-sensitive photographic silver halide emulsion containing a merocyanine dye which comprises two nuclei joined together through an acyclic methine group which is part of a polyene chain containing an equal number of alternating single and double bonds, one of the terminal atoms of said chain being the 2-carbon atom of an imidazo(4,5-b)quinoxaline nucleus, and the other terminal carbon atom of said polyene chain being in a second heterocyclic ring and attached to an extracyclic carbonylic oxygen atom.

11. A light-sensitive photographic silver halide emulsion containing a styryl dye which comprises an imidazo (4,5-b)quinoxoline nucleus joined to a para-alkylamino benzene ring through an acyclic polyene chain containing an equal number of single and double bonds, one terminal atom of said chain being the Z-carbon atom of said imidazo(4,5-b)quinoxaline nucleus, the other terminal carbon atom being in said benzene ring and attached to the nitrogen atom of said para-alkylamino group.

12. A light-sensitive photographic silver halide emulsion in accordance with claim 8 wherein said dye is a cyanine dye comprising two imidazo(4,5b)quinoxaline nuclei joined together through a polyene chain containing an equal number of alternating single and double bonds, the terminal carbon atom of said chain being the 2-carbon atom, respectively, of said imidazo(4,5-b)quinoxaline nuclei.

13. A light-sensitive photographic silver halide emulsion in accordance with claim 9 wherein said second nucleus is a desensitizing nucleus.

14. A light-sensitive photographic silver halide emulsion in accordance with claim 12 wherein said polyene chain is composed of 5 carbon atoms.

15. A silver halide emulsion containing a dye selected from the group consisting of 1,1,3 ,3 '-tetraethylimidazo [4,5 -b] quinoxalinocarbocyanine chloride;

1,1,3 ,3 '-tetraethylimidazo [4,5 -b] quinoxalinodicarbocyanine chloride;

1,3 ,3'-triethylimidazo [4,5 -b] quinoxalino-oxacarbocyanine iodide;

1,3,3 -triethylimidazo [4,5 -b] quinoxalino-thiacarbocyanine iodide;

l,3-diethyl-l,3 ,3-trirnethylimidazo [4,5-b] quinoxalinoindocarbocyanine iodide;

1,3-diethyl-3 -methylimidazo [4,5 -b] quinoxalinothiazolino-carbocyanine iodide;

1, 1 ,3-triethylimidazo [4,5 -b] quinoxalino-Z'-carbocyanine iodide;

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,451 ,111 March 4 1969 Leslie G S. Brooker et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 39, "opparent" should read apparent Column 6, lines 30 to 33, the formula should appear as shown below:

Column 7, lines 28 to 34, the right-hand portion of the formula should appear as shown below:

Column 11 line 42 "quinoxalinoethiacarbocyanine" should read quinoxalinothiacarbocyanine Column 14, line 64, "2-8- anilinovinyl-Zethylquinolinium" should read Z-B-anilinovinyll-ethylquinolinium Column 18, lines 47 to 54, the right-hand portion of the formula should appear as shown below:

-CH=CH I NMe Column 19, lines 55 to 61, the formula should appear as shown below:

lih N (:1 C1 CCH=CH-CH E1; Ph

OSO C H Column 21 line 5 after "in" insert pyridine and precipitating with methyl alcohol. A 79% yield of pure dye was obtained as dark brown crystals, M.P. 320. lines 49 to 51, cancel "pyridine and precipitating with methyl alcohol A 79% yield of pure dye was obtained as dark brown crystals M.P. 320 Column 24 line 70 "aceitc" should read acetic Column 26 line 19, "l,3-dially-6-chloro-2methylimidazo" should read 1,3- diallyl6chloro-2-methylimidazo Column 27 lines 2 to 6 that portion of the formula reading "-NPHh" should read NHPh Column 31 line 1 "at" should read as e Signed and sealed this 21st day of April 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

